Triester plasticizer composition and resin composition containing the same

Abstract

The present invention relates to a triester plasticizer composition, characterized by comprising a product of esterification of a mixture of hexanoic acid isomers with a triol, wherein the degree of branching of the mixture of hexanoic acid isomers is 2.0 or less. If the plasticizer composition is applied to a resin, the anti-migration property and the volatilization loss can be maintained at the same level compared with the case of applying a conventional plasticizer, and the mechanical properties, absorption rate, stress migration property, and plasticizing efficiency can be significantly improved.

Description

Technical Field

[0001] Cross - reference to Related Applications

[0002] This application claims the benefit of priority based on Korean Patent Application No. 10 - 2021 - 0080755, filed on June 22, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0004] The present invention relates to a plasticizer composition containing one or more triester groups and a resin composition containing the plasticizer composition. Background Art

[0005] Generally, plasticizers are obtained by the reaction of alcohols with polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. In addition, considering domestic and foreign regulations on phthalate plasticizers that are harmful to the human body, research on plasticizer compositions such as terephthalate, adipate, and other polymeric plasticizers that can replace phthalate plasticizers is ongoing.

[0006] Meanwhile, regardless of the industrial type, including the plastisol type industries such as floor materials, wallpapers, soft and hard sheets, the calendering type industries, or the extrusion / injection composite type industries, the demand for environmentally friendly products is increasing. In order to enhance the quality characteristics, processability, and productivity of the finished product, an appropriate plasticizer is required considering discoloration, migration, mechanical properties, etc.

[0007] According to the properties required by the industrial type in various application fields, such as tensile strength, elongation at break, light resistance, migration, gelling properties, and absorption rate, auxiliary materials such as plasticizers, fillers, stabilizers, viscosity reducers, dispersants, defoamers, and blowing agents are mixed with PVC resin.

[0008] For example, in a plasticizer composition applicable to PVC, when di(2 - ethylhexyl) terephthalate (DEHTP), which is relatively inexpensive and widely used, is applied, the hardness or sol viscosity is high, the absorption rate of the plasticizer is relatively slow, and the migration and stress migration are not good.

[0009] As an improvement to the above limitations, it is possible to consider applying the transesterification product with butanol as a composition containing DEHTP as a plasticizer. However, although the plasticizing efficiency is improved, the volatilization loss or thermal stability is poor, and the mechanical properties are slightly deteriorated, and physical properties need to be improved. Therefore, generally, there is no solution yet except for the method of compensating for the defects by mixing with a different second plasticizer.

[0010] However, in the case of applying a second plasticizer, there are drawbacks of generating the following unexpected defects: it is difficult to predict changes in physical properties; applying the second plasticizer may be a factor increasing the unit cost of the product; except for specific cases, the improvement in physical properties is not obvious; and problems related to the compatibility with the resin may occur.

[0011] In addition, if a substance such as tris(2-ethylhexyl) trimellitate or trisisononyl trimellitate is used as a trimellitate product to improve the poor migration and loss properties of a DEHTP product, the migration or loss properties may be improved, but the plasticizing efficiency may be reduced, and a large amount of this material needs to be injected to impart an appropriate plasticizing effect to the resin. Considering the relatively high unit price of the product, its commercialization is impossible.

[0012] Therefore, there is a need to develop a product for solving the environmental problems of conventional phthalate products, or a product for improving the poor physical properties of an environmentally friendly product (which is used to improve the environmental problems of phthalate products). Summary of the Invention

[0013] Technical Problem

[0014] The present invention provides a plasticizer composition which can maintain the same level of anti-migration and volatile loss as that of applying a conventional plasticizer, while significantly improving mechanical properties, absorption rate, stress migration, and plasticizing efficiency by containing a triester obtained from the esterification of a mixture of hexanoic acid isomers and a triol.

[0015] Technical Solution

[0016] To solve the above tasks, the present invention provides a plasticizer composition and a resin composition.

[0017] (1) The present invention provides a triester-based plasticizer composition containing one or more triesters of the following formula 1, wherein R1 to R3 in formula 1 are from a mixture of hexanoic acid isomers with a branching degree of 2.0 or less:

[0018] [Formula 1]

[0019]

[0020] In formula 1,

[0021] R1 to R3 are each independently a n-pentyl group, a branched pentyl group, or a cyclopentyl group,

[0022] R4 and R5 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

[0023] (2) The present invention provides the plasticizer composition according to (1), wherein the degree of branching of the hexanoic acid isomer mixture is 1.5 or less.

[0024] (3) The present invention provides the plasticizer composition according to (1) or (2), wherein the hexanoic acid isomer mixture contains 2-methylvaleric acid and 3-methylvaleric acid.

[0025] (4) The present invention provides the plasticizer composition according to any one of (1) to (3), wherein the hexanoic acid isomer mixture contains n-hexanoic acid, 2-methylvaleric acid, 3-methylvaleric acid, and cyclopentanecarboxylic acid.

[0026] (5) The present invention provides the plasticizer composition according to any one of (1) to (4), wherein, relative to 100 parts by weight of the hexanoic acid isomer mixture, the hexanoic acid isomer mixture contains 20 to 95 parts by weight of branched-chain hexanoic acid.

[0027] (6) The present invention provides the plasticizer composition according to any one of (1) to (5), wherein, relative to 100 parts by weight of the hexanoic acid isomer mixture, the hexanoic acid isomer mixture contains 30 parts by weight or less of cyclopentanecarboxylic acid.

[0028] (7) The present invention provides the plasticizer composition according to any one of (1) to (6), wherein, relative to 100 parts by weight of the hexanoic acid isomer mixture, the hexanoic acid isomer mixture contains 80 parts by weight or less of n-hexanoic acid.

[0029] (8) The present invention provides the plasticizer composition according to any one of (1) to (7), wherein R4 and R5 are hydrogen.

[0030] (9) The present invention provides a resin composition comprising: 100 parts by weight of a resin; and 5 to 150 parts by weight of the plasticizer composition according to any one of (1) to (8).

[0031] (10) The present invention provides the resin composition according to (9), wherein the resin is one or more selected from linear vinyl chloride polymers, paste vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrenes, polyurethanes, natural rubbers, and synthetic rubbers.

[0032] Advantageous Effects

[0033] The plasticizer composition according to an embodiment of the present invention, if used in a resin composition, can maintain the same level of anti-migration and volatile loss as a conventional plasticizer, and can significantly improve mechanical properties, absorption rate, stress migration, and plasticization efficiency. Detailed Description

[0034] It should be understood that the terms or words used in this disclosure and the claims should not be construed as having their conventional or dictionary definitions, but rather should be interpreted in accordance with the principle that the inventor can appropriately define the terms in order to best illustrate the invention, in a manner consistent with the technical scope of the present invention.

[0035] Definition of terms

[0036] As used in this disclosure, the term "composition" includes a mixture containing the corresponding constituent substances, as well as reaction products and decomposition products formed from the corresponding constituent substances.

[0037] As used in this disclosure, the term "isomer" is not intended to distinguish all meanings of isomers, but rather is intended to represent structural isomers, that is, the relationship of having the same number of carbons but different bonding structures, in order to distinguish these types, and does not represent substances that are classified as stereoisomers such as enantiomers and diastereomers.

[0038] As used in this disclosure, the term "linear vinyl chloride polymer" can be a type of vinyl chloride polymer and is obtained by polymerization such as suspension polymerization, bulk polymerization, etc., and can refer to a polymer having a porous particle shape in which a large number of pores with sizes of dozens to hundreds of micrometers are dispersed, having no cohesion and excellent fluidity.

[0039] As used in this disclosure, the term "paste vinyl chloride polymer" can be a type of vinyl chloride polymer and is obtained by polymerization such as micro-suspension polymerization, micro-seed polymerization, emulsion polymerization, etc., and can refer to a polymer having minute particles without pores and with sizes of dozens to thousands of nanometers, having cohesion and poor fluidity.

[0040] The terms "comprising" and "having" and their derivatives in the present invention, although whether these terms are specifically disclosed or not, are not intended to exclude the presence of optional additional ingredients, steps or processes. To avoid any uncertainty, unless otherwise described to the contrary, all compositions claimed by using the term "comprising" can contain optional additional additives, auxiliaries or compounds, including polymers or any other substances. In contrast, the term "consisting essentially of" excludes those that are unnecessary for the operation from the optionally continuously described scope, and excludes optional other ingredients, steps or processes. The term "consisting of" excludes optional ingredients, steps or processes that are not specifically described or listed.

[0041] Measurement method

[0042] In the present disclosure, the content analysis of the components in the composition is carried out by gas chromatography measurement using a gas chromatography device of Agilent Co. (product name: Agilent 7890GC, column: HP-5, carrier gas: helium (flow rate: 2.4 mL / min), detector: F.I.D., injection volume: 1 μL, initial value: 70 °C / 4.2 min, final value: 280 °C / 7.8 min, program rate: 15 °C / min).

[0043] In the present disclosure, "hardness" refers to the Shore hardness (Shore "A" and / or Shore "D") at 25 °C and is measured under the conditions of 3T 10s using ASTM D2240. Hardness can be an index for evaluating the plasticizing efficiency, and the lower the value, the better the plasticizing efficiency.

[0044] In the present disclosure, the "tensile strength" is obtained according to the ASTM D638 method as follows: Using a U.T.M test device (manufacturer: Instron, model name: 4466), the specimen is stretched at a crosshead speed of 200 mm / min (1T), the position of the fracture of the specimen is measured, and it is calculated according to the following mathematical formula 1:

[0045] [Mathematical formula 1]

[0046] Tensile strength (kgf / cm 2 ) = Load value (kgf) / Thickness (cm) × Width (cm)

[0047] In the present disclosure, the "elongation at break" is obtained according to the ASTM D638 method as follows: Using a U.T.M, the specimen is stretched at a crosshead speed of 200 mm / min (1T), the position of the fracture of the specimen is measured, and it is calculated according to the following mathematical formula 2:

[0048] [Mathematical formula 2]

[0049] Elongation at break (%) = Length after elongation / Initial length × 100

[0050] In the present disclosure, the "migration loss" is obtained according to KSM-3156. According to KSM-3156, a specimen with a thickness of 2 mm or more is obtained, glass plates are adhered to both sides of the specimen, and a load of 1 kgf / cm 2 is applied. The specimen is placed in a hot air circulation type oven (80 °C) for 72 hours, then taken out and cooled at room temperature for 4 hours. Then, the glass plates adhered to both sides of the specimen are removed, the weights of the glass plates and the specimen plates before and after being placed in the oven are measured, and the migration loss is calculated according to the following mathematical formula 3.

[0051] [Mathematical formula 3]

[0052] Migration loss (%) = {[(weight of the initial sample) - (weight of the sample after being placed in the oven)] / (weight of the initial sample)} × 100

[0053] In the present disclosure, "volatile loss" is obtained by treating the sample at 80 °C for 72 hours and then measuring the weight of the sample.

[0054] [Mathematical formula 4]

[0055] Volatile loss (wt%) = {[(weight of the initial sample) - (weight of the sample after treatment)] / (weight of the initial sample)} × 100

[0056] In the case of various measurement conditions, the detailed description of conditions such as temperature, rotation speed, time, etc. can vary slightly according to the situation, and if the conditions are different, the measurement method and its conditions need to be specified separately.

[0057] Hereinafter, the present invention will be described in more detail to facilitate the understanding of the present invention.

[0058] According to an embodiment of the present invention, a plasticizer composition comprises one or more triesters of the following formula l, wherein the alkyl groups of the triesters are from a mixture of hexanoic acid isomers having a degree of branching of 2.0 or less.

[0059] [Formula 1]

[0060]

[0061] In Formula 1, R1 to R3 are each independently a n-pentyl group, a branched pentyl group or a cyclopentyl group, and R4 and R5 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

[0062] The plasticizer composition can be a product prepared by the esterification of a mixture of hexanoic acid isomers and a triol, and thus can be derived from a carboxylic acid having a carbon chain of 6 carbon atoms with a carbonyl as the central carbon. As R1 to R3 in Formula 1, a straight-chain, branched-chain or alicyclic alkyl group having 5 carbon atoms can be applied.

[0063] The plasticizer composition according to an embodiment of the present invention comprises one or more triesters represented by Formula 1, wherein the number of triesters finally produced can be determined according to the number of hexanoic acids contained in the mixture of hexanoic acid isomers used for esterification. For example, if the mixture of hexanoic acid isomers includes two types of isomers, at least five types of triesters can be included in the plasticizer composition, and if three types of isomers are included, at least 15 types of triesters can be included in the plasticizer composition.

[0064] In a plasticizer composition according to an embodiment of the present invention, an alkyl carboxylic acid having 6 carbon atoms, namely caproic acid, is specifically applied. Compared with the case of applying other carbon numbers, the plasticizing efficiency and mechanical properties can be improved simultaneously. If an alkyl carboxylic acid having 5 or less carbon atoms is applied, the mechanical properties and stress migration properties may be reduced, and if an alkyl carboxylic acid having 7 or more carbon atoms is applied, the plasticizing efficiency may be poor, the absorption rate may be very slow, and the processability may be significantly deteriorated.

[0065] In addition, considering a compound having three ester groups as a triester, the plasticizer composition has excellent compatibility with resins and excellent miscibility with other additives, and has many ester groups to fix molecules in the polymer chain. Therefore, it can have excellent plasticizing efficiency and mechanical properties while maintaining an appropriate level of anti-migration property and volatilization loss.

[0066] In addition, different from the case where a benzene ring is present in the molecule as in petroleum-based plasticizers, there is no benzene ring in the molecule. When compared with petroleum-based plasticizers, the plasticizer can be classified as an environmentally friendly plasticizer and is evaluated to have excellent properties. These effects are understood due to the preparation of the plasticizer by the reaction of a polyol and a monocarboxylic acid, which is different from the conventional preparation of plasticizers by the reaction of a polycarboxylic acid and a monohydric alcohol.

[0067] The alkyl group of the triester contained in the plasticizer composition according to an embodiment of the present invention may be derived from a mixture of caproic acid isomers having a degree of branching of 2.0 or less, preferably 1.5 or less, 1.3 or less, 1.2 or less, or 1.0 or less. In addition, the degree of branching may be 0.1 or more, 0.2 or more, or 0.3 or more.

[0068] Here, the degree of branching may refer to how many branched-chain carbon atoms the alkyl group bonded to the substance contained in the composition has, and may be determined according to the weight ratio of the corresponding substances. For example, if the caproic acid mixture contains 60% by weight of 1-caproic acid, 30% by weight of 2-methylvaleric acid, and 10% by weight of 2-ethylbutyric acid, the branched-chain carbon numbers of the respective carboxylic acids are 0, 1, and 2, and the degree of branching can be calculated by [(60×0)+(30×1)+(10×2)] / 100 and can be 0.5. At the same time, in the present invention, the branched-chain carbon number of cyclopentanecarboxylic acid is considered to be 0.

[0069] Specifically, according to the proportion of branched-chain alkyl groups present in all alkyl groups, and further, the proportion of specific branched-chain alkyl groups present in the branched-chain alkyl groups, the physical properties of plasticizing efficiency and anti-migration property / volatilization loss can be balanced, and even further, the processability can be optimized. In addition, according to the interaction between various triesters contained in the composition, mechanical properties such as tensile strength and elongation at break, and stress resistance can be significantly improved.

[0070] In this way, it is possible to achieve a material that has no environmental problems at all, and at the same time, a product that can significantly improve the tensile strength of conventional phthalate products, a product that can significantly improve the migration resistance and stress resistance of conventional terephthalate products, and a product that can achieve balanced physical properties and a significantly improved level of physical properties compared to conventional commercial products.

[0071] According to one embodiment of the present invention, in order to optimally and advantageously achieve the above effects, the hexanoic acid isomer mixture may substantially comprise 2-methylvaleric acid and 3-methylvaleric acid. By substantially comprising these two isomers among the various isomers in the isomer mixture, the above effects can be achieved with higher reproducibility.

[0072] In addition, in addition to 2-methylvaleric acid and 3-methylvaleric acid, the hexanoic acid isomer mixture may further comprise n-hexanoic acid and cyclopentanecarboxylic acid. In the case of n-hexanoic acid, with the inclusion of n-hexanoic acid, specific physical properties tend to improve, but considering the processing properties such as the absorption rate or plasticizing efficiency, its dosage needs to be controlled, and the same applies to cyclopentanecarboxylic acid.

[0073] In a plasticizer composition according to one embodiment of the present invention, in the hexanoic acid isomer mixture, with respect to a total of 100 parts by weight of this mixture, the content of branched-chain hexanoic acid may be 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, and 95 parts by weight or less, 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, or 70 parts by weight or less.

[0074] In addition, with respect to a total of 100 parts by weight of the hexanoic acid isomer mixture, the content of n-hexanoic acid may be 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, or 30 parts by weight or less, and 1 part by weight or more, 2 parts by weight or more, 5 parts by weight or more, or 10 parts by weight or more.

[0075] The contents of the branched-chain and straight-chain types can be appropriately adjusted according to the application uses of the triester plasticizer, and by adjusting this ratio, the desired physical properties can be achieved.

[0076] In addition, the isomer mixture may further comprise cyclopentanecarboxylic acid. In this case, with respect to a total of 100 parts by weight of the isomer mixture, it may be included in an amount of 30 parts by weight or less. Preferably, it may be included in an amount of 20 parts by weight or less, 15 parts by weight or less. In the case of cyclopentanecarboxylic acid, as long as cyclopentanecarboxylic acid is included, improvement in processing properties and mechanical properties can be achieved, and its content can be adjusted in consideration of the deterioration of physical properties caused by the reduction of the relative content of other isomers.

[0077] In the mixture of hexanoic acid isomers for determining the degree of branching of a plasticizer composition according to an embodiment of the present invention, a variety of isomers can be included, usually the four types of isomers mentioned, without excluding the presence of other isomers. For example, 4-methylpentanoic acid, 2-ethylbutyric acid, 2,3-dimethylbutyric acid, etc. can be included. In addition, structural isomers of C6 alkyl carboxylic acids can be present.

[0078] In addition, the plasticizer composition according to an embodiment of the present invention is derived from the reaction of the above-mentioned mixture of hexanoic acid isomers and a triol, and the triol can be a glycerol compound and can be represented by, for example, the following formula 2.

[0079] [Formula 2]

[0080]

[0081] In formula 2, R4 and R5 are the same as those defined in formula 1.

[0082] R4 and R5 can each independently be hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl, and most preferably glycerol in which both R4 and R5 are hydrogen. Considering that glycerol is easily supplied, it can be synthesized from natural materials and is a substance easily obtained by other synthetic methods. Glycerol can contribute to improving the price competitiveness of the plasticizer.

[0083] The method for preparing the plasticizer composition according to an embodiment of the present invention is a method well known in the art, and any method capable of preparing the above-mentioned plasticizer composition can be applied without specific limitation.

[0084] That is, by appropriately controlling the esterification reaction, the plasticizer composition according to the present invention can be prepared. For example, the composition can be prepared by direct esterification of a mixture of hexanoic acid isomers and a glycerol compound represented by formula 2 (for example, glycerol).

[0085] The plasticizer composition according to an embodiment of the present invention is a substance prepared by appropriately performing an esterification reaction, and any preparation method that satisfies the above conditions, specifically, controls the proportion of branched-chain hexanoic acid in the isomer mixture, can be applied without particular limitation.

[0086] For example, the direct esterification can be carried out through the following steps: the step of injecting a mixture of hexanoic acid isomers and a glycerol compound represented by formula 2, adding a catalyst and reacting in a nitrogen atmosphere; the step of removing unreacted alcohol and neutralizing unreacted acid; and the step of dehydrating by distillation and filtering under reduced pressure.

[0087] The case of the mixture of hexanoic acid isomers, i.e., monocarboxylic acids, can play a major role in determining the component ratio in the prepared composition, and the theoretical molar ratio with glycerol compounds can be applied as 3:1. If the mixture of hexanoic acid isomers greater than the above molar ratio is additionally injected, the reaction rate can be increased. In this case, the additional injection amount of the mixture of hexanoic acid isomers can be 400 mol% or less, or 300 mol% or less, preferably 200 mol% or less or 100 mol% or less, relative to the equivalent of the mixture of hexanoic acid isomers.

[0088] The catalyst can be, for example, at least one or more selected from the following: acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid and alkyl sulfates; metal salts such as aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, iron chloride and aluminum phosphate; metal oxides such as heteropolyacids, natural / synthetic zeolites, cation and anion exchange resins; and organometals such as tetraalkyl titanates and their polymers. In a specific embodiment, tetraalkyl titanates can be used as the catalyst. Preferably, as acid catalysts with low activation temperatures, p-toluenesulfonic acid and methanesulfonic acid can be suitable.

[0089] The amount of the catalyst can vary depending on the type. For example, based on a total of 100% by weight of the reactants, the homogeneous catalyst can be used in the range of 0.01% to 5.00% by weight, 0.01% to 3.00% by weight, 0.1% to 3.0% by weight or 0.1% to 2.0% by weight, while based on the total amount of the reactants, the heterogeneous catalyst can be used in the range of 5% to 200% by weight, 5% to 100% by weight, 20% to 200% by weight or 20% to 150% by weight.

[0090] In this case, the reaction temperature can be in the range of 100 °C to 280 °C, 100 °C to 250 °C or 100 °C to 230 °C.

[0091] According to another embodiment of the present invention, a resin composition comprising the plasticizer composition and a resin is provided.

[0092] The resin can be a resin known in the art. For example, a mixture of one or more selected from linear vinyl chloride polymers, paste vinyl chloride polymers, ethylene vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrenes, polyurethanes, natural rubbers, synthetic rubbers and thermoplastic elastomers can be used without limitation.

[0093] Based on 100 parts by weight of the resin, the content of the plasticizer composition can be from 5 parts by weight to 150 parts by weight, preferably from 5 parts by weight to 130 parts by weight or from 10 parts by weight to 120 parts by weight.

[0094] Generally, the resin using the plasticizer composition can be prepared into a resin product by melt processing or plastisol processing, and the resin by melt processing and the resin by plastisol processing can be prepared differently according to their respective polymerization methods.

[0095] For example, in the case of using a vinyl chloride polymer in melt processing, a solid resin particle having a large average particle size is prepared by suspension polymerization or the like and used, and this vinyl chloride polymer is called a linear vinyl chloride polymer. In the case of using a vinyl chloride polymer in plastisol processing, a resin in the form of a sol state as minute resin particles is prepared by emulsion polymerization or the like and used, and this vinyl chloride polymer is called a paste vinyl chloride resin.

[0096] In the case of a linear vinyl chloride polymer, the plasticizer can be included in the range of 5 parts by weight to 80 parts by weight relative to 100 parts by weight of the polymer, while in the case of a paste vinyl chloride polymer, the plasticizer can be included in the range of 40 parts by weight to 120 parts by weight relative to 100 parts by weight of the polymer.

[0097] The resin composition may further contain a filler. Based on 100 parts by weight of the resin, the filler can be from 0 parts by weight to 300 parts by weight, preferably from 50 parts by weight to 200 parts by weight, more preferably from 100 parts by weight to 200 parts by weight.

[0098] The filler can use fillers known in the art and is not specifically limited. For example, the filler can be a mixture of one or more types selected from silica, magnesium carbonate, calcium carbonate, lignite, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate, and barium sulfate.

[0099] In addition, as needed, the resin composition may further contain other additives such as a stabilizer. Based on 100 parts by weight of the resin, each of the other additives such as a stabilizer can be, for example, from 0 parts by weight to 20 parts by weight, preferably from 1 part by weight to 15 parts by weight.

[0100] The stabilizer can use, for example, a calcium-zinc type (Ca-Zn type) stabilizer such as a composite stearate of calcium and zinc, or a barium-zinc type (Ba-Zn type) stabilizer, but the stabilizer is not specifically limited.

[0101] As described above, the resin composition can be applied to both melt processing and plastisol processing, and calendering, extrusion, or injection processing can be applied to melt processing, while coating processing or the like can be applied to plastisol processing.

[0102] Example

[0103] Hereinafter, examples will be described in detail to specifically illustrate the present invention. However, the present invention can be implemented in different forms and should not be construed as limited to the examples set forth herein. On the contrary, these examples are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the inventive concept to those skilled in the art.

[0104] Example 1

[0105] Into a reactor equipped with a stirrer, a condenser, and a decanter, 1360 g of a mixture containing about 9 wt% of 1-hexanoic acid, about 35 wt% of 2-methylpentanoic acid, about 44 wt% of 3-methylpentanoic acid, about 7 wt% of 4-methylpentanoic acid, and about 5 wt% of cyclopentanecarboxylic acid as a mixture of hexanoic acid isomers, 276 g of glycerol, and 5 g of methanesulfonic acid were added, and an esterification reaction was carried out at a reaction temperature of 100 °C to 140 °C under a nitrogen atmosphere. After the reaction was completed, unreacted acids were removed, the catalyst and the product were neutralized with an aqueous alkaline solution, and washed. Unreacted raw materials and moisture were separated, and finally a triester plasticizer composition was obtained.

[0106] Example 2

[0107] A triester plasticizer composition was obtained by the same method as in Example 1, except that 1360 g of a mixture containing about 20 wt% of 1-hexanoic acid, about 30 wt% of 2-methylpentanoic acid, about 35 wt% of 3-methylpentanoic acid, about 5 wt% of 4-methylpentanoic acid, and about 10 wt% of cyclopentanecarboxylic acid was used as the mixture of hexanoic acid isomers.

[0108] Example 3

[0109] A triester plasticizer composition was obtained by the same method as in Example 1, except that 1360 g of a mixture containing about 2 wt% of 1-hexanoic acid, about 40 wt% of 2-methylpentanoic acid, about 50 wt% of 3-methylpentanoic acid, about 2 wt% of 4-methylpentanoic acid, and about 6 wt% of cyclopentanecarboxylic acid was used as the mixture of hexanoic acid isomers.

[0110] Example 4

[0111] A triester plasticizer composition was obtained by the same method as in Example 1, except that a mixture containing 1360 g of about 5 wt% 1-hexanoic acid, about 50 wt% 2-methylvaleric acid, about 30 wt% 3-methylvaleric acid, and about 15 wt% cyclopentanecarboxylic acid was used as the hexanoic acid isomer mixture.

[0112] Comparative Example 1

[0113] Dioctyl phthalate (DOP, LG Chem) was used as the plasticizer.

[0114] Comparative Example 2

[0115] Diisononyl phthalate (DINP, LG Chem) was used as the plasticizer.

[0116] Comparative Example 3

[0117] Product GL300 of LG Chem, which is dioctyl terephthalate, was used as the plasticizer.

[0118] Comparative Example 4

[0119] Product GL500 of LG Chem, which is a mixture of dibutyl terephthalate, butyl octyl terephthalate, and dioctyl terephthalate, was used as the plasticizer.

[0120] Comparative Example 5

[0121] A triester plasticizer composition was obtained by the same method as in Example 1, except that a 7:3 acid mixture of n-butyric acid and benzoic acid by weight was used instead of the hexanoic acid isomer mixture.

[0122] Comparative Example 6

[0123] A triester plasticizer composition was obtained by the same method as in Example 1, except that 1360 g of the single compound 3-methylvaleric acid was used instead of the hexanoic acid isomer mixture.

[0124] Comparative Example 7

[0125] A triester plasticizer composition was obtained by the same method as in Example 1, except that 1030 g of n-butyric acid was used instead of the hexanoic acid isomer mixture.

[0126] Comparative Example 8

[0127] A triester plasticizer composition was obtained by the same method as in Example 1, except that 1523 g of n-heptanoic acid was used instead of the hexanoic acid isomer mixture.

[0128] Comparative Example 9

[0129] A triester plasticizer composition was obtained by the same method as in Example 1, except that an acid mixture of 1-caproic acid and 2-ethylhexanoic acid, each at 50 wt% and with a total of 1520 g, was used instead of the caproic acid isomer mixture.

[0130] The types and amounts of acids used in the examples and comparative examples, as well as the degree of branching of the acid mixtures, are summarized in Table 1 below.

[0131] [Table 1]

[0132]

[0133] Experimental Example 1: Evaluation of the properties of the sheet

[0134] Specimens were manufactured according to ASTM D638 and the following formulation and manufacturing conditions using the plasticizers of the examples and comparative examples.

[0135] (1) Formulation: 100 parts by weight of linear vinyl chloride polymer (LS100), 50 parts by weight of plasticizer, and 3 parts by weight of stabilizer (BZ-153T)

[0136] (2) Mixing: Mixing at 98 °C and 700 rpm

[0137] (3) Manufacturing specimens: 1T sheets, 2T sheets, and 3T sheets were manufactured by processing for 4 minutes at 160 °C using a roll mill and then processing for 2.5 minutes (low pressure) and 2 minutes (high pressure) at 180 °C using a press.

[0138] (4) Test items

[0139] 1) Hardness : Using ASTM D2240, the Shore hardness (Shore "A" and Shore "D") at 25 °C was measured for 10 seconds using a 3T specimen. If the value is small, the plasticizing efficiency is evaluated as excellent.

[0140] 2) Tensile strength : By the ASTM D638 method, the specimen was stretched using a U.T.M test device (manufacturer: Instron, model name: 4466) at a crosshead speed of 200 mm / min, and the position of the fracture of the 1T specimen was measured. The tensile strength was calculated by the following mathematical formula 1.

[0141] [Mathematical formula 1]

[0142] Tensile strength (kgf / cm 2 ) = Load value (kgf) / Thickness (cm) × Width (cm)

[0143] 3) Measurement of elongation at break: Using a U.T.M. test apparatus, the specimen was stretched at a crosshead speed of 200 mm / min in accordance with ASTM D638 method, and the position of the fracture of the 1T specimen was measured. The elongation was calculated by the following mathematical formula 2.

[0144] [Mathematical formula 2]

[0145] Elongation (%) = (Length after elongation) / (Initial length) × 100

[0146] 4) Measurement of migration loss : According to KSM-3156, specimens with a thickness of 2 mm or more were obtained. Glass plates were adhered to both sides of the 1T specimen, and a load of 1 kgf / cm 2 was applied. The specimens were placed in a hot air circulation oven (80 °C) for 72 hours, then taken out and cooled at room temperature for 4 hours. Then, the glass plates adhered to both sides of the specimens were removed, and the weights of the specimens before and after placing the glass plates and the specimen plates in the oven were measured, and the migration loss was calculated by the following mathematical formula 3.

[0147] [Mathematical formula 3]

[0148] Migration loss (%) = {[(Weight of the initial specimen) - (Weight of the specimen after being placed in the oven)] / (Weight of the initial specimen)} × 100

[0149] 5) Measurement of volatile loss : The manufactured specimens were treated at 80 °C for 72 hours, the weights of the specimens were measured, and the measurement was carried out by the following mathematical formula 4.

[0150] [Mathematical formula 4]

[0151] Volatile loss (weight %) = [{(Weight of the initial specimen) - (Weight of the specimen after treatment)} / (Weight of the initial specimen)] × 100

[0152] 6) Stress test (stress resistance) : Specimens with a thickness of 2 mm in the bent state were placed at 23 °C for 168 hours, and the degree of migration (exudation degree) was observed. The results were recorded as numerical values. If the numerical values were close to 0, it indicated excellent performance.

[0153] 7) Measurement of absorption rate

[0154] The absorption rate was evaluated by measuring the time required to mix the resin with the ester compound and stabilize the torque of the mixer using a planetary mixer (Brabender, P600) at 73 °C and 60 rpm. As a reference, if the absorption rate is measured to be less than 4 minutes, it appears that the absorption and migration of the plasticizer are repeated during processing; if the absorption rate is greater than 9 minutes, it is considered that absorption hardly occurs. Therefore, if a value between 4 minutes and 9 minutes is not measured, it is evaluated as not processable.

[0155] (5) Evaluation results

[0156] The evaluation results of the test items are shown in Table 2 below.

[0157] [Table 2]

[0158]

[0159] Referring to the results in Table 2, it can be confirmed that when compared with Comparative Examples 1 and 2 which are conventional phthalate products, the plasticizer composition according to the embodiments of the present invention exhibits very excellent plasticizing efficiency and significantly improved absorption rate, and even has a significantly high elongation at break; even when compared with Comparative Examples 3 and 4 which are environmentally friendly products, significant improvements in plasticizing efficiency, migration loss, and volatilization loss are observed, and further significant improvements in stress resistance. In addition, by simultaneously having excellent plasticizing efficiency and absorption rate, it can be confirmed that the plasticizer composition of the present invention has very excellent processing performance, is suitable for large-scale production, and is a stable product.

[0160] Furthermore, it can be confirmed that when compared with the plasticizers of Comparative Examples 1 and 2 which are conventional phthalate plasticizers with high performance but causing fatal environmental problems, the plasticizing composition of the present invention reaches the same or better level, and the plasticizing composition of the present invention is very suitable as a substitute.

[0161] In addition, compared with the examples of the present invention, Comparative Example 5, in which the esterification product of glycerol and an acid was used, but a mixture of n-butyric acid and benzoic acid was used instead of the mixture of hexanoic acid isomers as the acid, showed a significantly low elongation rate and showed significantly worse results in terms of volatile loss compared with the examples of the present invention. In addition, in the case of Comparative Example 5, in the experiment for measuring the absorption rate, intractable results were shown. In addition, compared with the examples, Comparative Example 9 using a mixture of hexanoic acid and 2-ethylhexanoic acid as the acid showed significantly worse plasticizing efficiency, as well as significantly worse elongation rate, migration loss, stress resistance, and absorption rate compared with the examples. From these results, it can be confirmed that the improvement effect achieved by the plasticizer composition of the present invention is not due to the application of other acids, but due to the application of hexanoic acid having 6 carbon atoms. Specifically, it can be confirmed that it is due to the use of the isomer mixture type of hexanoic acid.

[0162] Meanwhile, compared with the examples, Comparative Example 6, in which hexanoic acid was used, but it was used not as an isomer mixture type but as a single compound, showed a poor elongation rate and showed slightly worse volatile loss compared with the examples. In addition, compared with the examples, Comparative Example 7 using n-butyric acid having 4 carbon atoms showed significantly worse results in all aspects of tensile strength, elongation rate, migration loss, and volatile loss, and also showed intractability for the absorption rate. Finally, compared with the examples, Comparative Example 8 using n-heptanoic acid having 7 carbon atoms showed significantly worse plasticizing efficiency due to high hardness, and showed worse results in terms of elongation rate, migration loss, and stress resistance compared with the examples. The absorption rate was also slightly worse compared with the examples. From these results, it can be confirmed that, as in the examples of the present invention, it is necessary to use the hexanoic acid isomer mixture to achieve excellent plasticizing efficiency, mechanical properties, and various properties such as balanced stress resistance and processability, and in the case of applying an acid having a carbon number different from that of hexanoic acid (Comparative Example 7 and Comparative Example 8), or in the case of applying only one type of hexanoic acid (Comparative Example 6), this improved effect cannot be achieved.

[0163] Experimental Example 2: Evaluation of the properties of plastisol

[0164] Specimens were manufactured according to ASTM D638 and the following formulation and manufacturing conditions by using the plasticizers of the examples and comparative examples.

[0165] (1) Formulation: 100 parts by weight of a paste polyvinyl chloride polymer (KH-10), 70 parts by weight of a plasticizer, 3 parts by weight of a stabilizer (BZ-119), 3 parts by weight of a foaming agent (AC5000), and 40 parts by weight of a filler (OMYA-10)

[0166] (2) Mixing: Mix for 15 minutes at 1000 rpm

[0167] (3) Test Items

[0168] 1) Viscosity : Using a Brookfield (LV type) viscometer, measure with Brookfield viscosity. Use #64 as the rotor, measurement rates are 6 rpm and 60 rpm, and measurement temperatures are 25 °C and 40 °C.

[0169] (4) Evaluation Results

[0170] The evaluation results of the test items are shown in Table 3 below.

[0171] [Table 3]

[0172]

[0173] Referring to the results in Table 3, it can be found that the plasticizer compositions of Examples 1 to 4 exhibit very low initial viscosities during plastisol processing, and the processing is very favorable, and also exhibit small viscosity changes over time, with excellent viscosity stability. However, it can be found that Comparative Examples 1 to 4 corresponding to the conventional products themselves exhibit high viscosities, and compared with the examples, the plastisol processing is very unfavorable. Specifically, in the case of Comparative Examples 1 to 4, the viscosity change is large, the initial viscosity is also large, and it can be confirmed that the performance is significantly worse in plastisol processing compared with the plasticizer compositions of the present invention.

[0174] Meanwhile, it can be confirmed that in Comparative Examples 5 to 9, where a plasticizer composition similar to the present invention is used and the esterification reaction of glycerol is used to prepare the plasticized composition, but different acids are used, Comparative Examples 5 to 9 exhibit poor performance in plastisol processing compared to the examples of the present invention. Specifically, in the case of Comparative Example 5 where n-butyric acid and benzoic acid are mixed and used, the initial viscosity is about 4 times higher than that of the examples of the present invention, and the processing itself cannot be carried out, and the viscosity change over time is also high, and the viscosity stability deteriorates. In the case of Comparative Example 6, where an acid having 6 carbon atoms is used similarly to the examples of the present invention, but 3-methylvaleric acid is used alone instead of the isomer mixture, both the initial viscosity and the viscosity stability exhibit levels similar to those of the examples, but under the conditions of plastisol processing at a relatively high temperature of 40 °C, it can be confirmed that the viscosity change over time is slightly increased compared to the plasticizer composition of the examples. From these results, it can be inferred that if an acid having 6 carbon atoms is used, but in the form of an isomer mixture, the effect of improving viscosity stability can be achieved. In addition, in the case of Comparative Example 7 where an acid having 4 carbon atoms is used, the highest initial viscosity is exhibited, and it is found that Comparative Example 7 is not suitable for plastisol processing. In the case of Comparative Example 8 where an acid having 7 carbon atoms is used, the initial viscosity and viscosity stability at low rpm are similar to those of the examples, but the viscosity stability at high rpm is worse than that of the examples. Finally, in Comparative Example 9, where caproic acid having 6 carbon atoms is used, but is used by mixing with 2-ethylhexanoic acid having 8 carbon atoms, Comparative Example 9 shows slightly worse results in terms of the overall initial viscosity and viscosity stability compared to the examples.

[0175] From the above results, it can be confirmed that the plasticizer composition of the present invention uses an acid having 6 carbon atoms in the form of an isomer mixture, and excellent processing performance and viscosity stability can be achieved even in plastisol processing.

Claims

1. A triester plasticizer composition comprising: One or more triesters of the following formula 1, Among them, In formula 1, R1 to R3 are from a mixture of hexanoic acid isomers having a degree of branching of 0.3 or more and 2.0 or less, wherein the mixture of hexanoic acid isomers comprises 1-hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid and cyclopentanecarboxylic acid: [Formula 1] In formula 1, R1 to R3 are each independently n-pentyl, branched pentyl or cyclopentyl, R4 and R5 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, wherein the mixture of hexanoic acid isomers comprises 20 to 95 parts by weight of branched hexanoic acid relative to a total of 100 parts by weight of the mixture, wherein the mixture of hexanoic acid isomers comprises 30 parts by weight or less of cyclopentanecarboxylic acid relative to a total of 100 parts by weight of the mixture, wherein the mixture of hexanoic acid isomers comprises 80 parts by weight or less of 1-hexanoic acid relative to a total of 100 parts by weight of the mixture, wherein the composition is prepared by direct esterification of the mixture of hexanoic acid isomers with a glycerol compound represented by formula 2, [Formula 2] wherein R4 and R5 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

2. The plasticizer composition according to claim 1, wherein The degree of branching of the mixture of hexanoic acid isomers is 1.5 or less.

3. The plasticizer composition according to claim 1, wherein R4 and R5 are hydrogen.

4. A resin composition comprising: 100 parts by weight of a resin; and 5 to 150 parts by weight of the plasticizer composition according to claim 1.

5. The resin composition according to claim 4, wherein, The resin is one or more selected from linear vinyl chloride polymers, paste vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrenes, polyurethanes, natural rubbers and synthetic rubbers.

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